Department of Polymer Science and Engineering, University of Massachusetts, Amherst, Massachusetts 01003, USA.
J Chem Phys. 2018 Oct 28;149(16):163306. doi: 10.1063/1.5029980.
We study the translocation of charged star polymers through a solid-state nanopore using coarse-grained Langevin dynamics simulations, in the context of using nanopores as high-throughput devices to characterize polymers based on their architecture. The translocation is driven by an externally applied electric field. Our key observation is that translocation kinetics is highly sensitive to the functionality (number of arms) of the star polymer. The mean translocation time is found to vary non-monotonically with polymer functionality, exhibiting a critical value for which translocation is the fastest. The origin of this effect lies in the competition between the higher driving force inside the nanopore and inter-arm electrostatic repulsion in entering the pore, as the functionality is increased. Our simulations also show that the value of the critical functionality can be tuned by varying nanopore dimensions. Moreover, for narrow nanopores, star polymers above a threshold functionality do not translocate at all. These observations suggest the use of nanopores as a high-throughput low-cost analytical tool to characterize and separate star polymers.
我们使用粗粒郎之万动力学模拟研究了带电荷的星形聚合物在固态纳米孔中的输运,其背景是将纳米孔用作高通量设备,根据聚合物的结构对其进行特性分析。输运由外加电场驱动。我们的主要观察结果是,输运动力学对星形聚合物的官能度(臂数)非常敏感。发现平均输运时间随聚合物官能度的变化呈非单调变化,在某个临界值下,输运速度最快。这种效应的起源在于纳米孔内的驱动力和进入孔内时的臂间静电排斥之间的竞争,随着官能度的增加而加剧。我们的模拟还表明,可以通过改变纳米孔的尺寸来调整临界官能度的值。此外,对于较窄的纳米孔,高于临界官能度的星形聚合物根本不会发生输运。这些观察结果表明,可以将纳米孔用作高通量、低成本的分析工具来对星形聚合物进行特性分析和分离。